Umpolung Synthesis of Diarylmethylamines via Palladium-Catalyzed Arylation of N-Benzyl Aldimines.

An umpolung synthesis of diarylmethylamine derivatives is presented. This reaction entails a Pd catalyzed arylation of 1,3-diaryl-2-azaallyl anions, in situ generated from N-benzyl aldimines. A Pd(NIXANTPHOS)-based catalyst together with hindered silylamide bases enabled the coupling of aldimines with aryl bromides in good to excellent yields without product isomerization. Moreover, regioselectivity in the arylation of unsymmetrical 1,3-diaryl-2-azaallyl anions was studied. This method is suitable for a gram scale synthesis of diarylmethylamine derivatives at room temperature without use of a glovebox.

Prospective evaluation of complications in laparoscopic urology at a mid-volume institution using standardized criteria: Experience of 1023 cases including learning curve in 9 years.

AIM: To evaluate the laparoscopic operations performed in our department according to the modified Clavien classification system of complications. MATERIALS AND METHODS: Between September, 2005 and February, 2014, a total of 1023 laparoscopic cases were performed. This period was divided into three terms (Terms 1, 2 and 3 consisting of 38, 32 and 32 months, respectively). According to the European Scoring System (ESS), easy (E), slightly difficult (SD), fairly difficult (FD), difficult (D), very difficult (VD) and extremely difficult (ED) cases were 35, 88, 170, 390, 203 and 137, respectively. The perioperative complications were evaluated based on the 3 time periods, with a specific emphasis on determining the learning curve according to the modified Clavien classification system of complications. RESULTS: A total of 236 (23.1%) complications were observed according to the modified Clavien classification. The minor (Clavien I-II) and major (Clavien III, IV and V) complication rates were 20.5% (n = 210) and 2.4% (n = 26), respectively. Clavien I was the most frequently encountered type of complication (n = 120, %11.7). No significant difference was observed among all 3 time periods regarding total complication rates. The D cases had the highest complication rate compared to E, SD, FD, VD and ED cases among all three terms. The total number of complications increased significantly with increasing grade of technical difficulty according to the ESS. CONCLUSION: Complications encountered in our laparoscopic surgery experience were predominantly minor, and the rate of complications was not significantly increased during the learning curve. The present data can provide guidance and manage expectations for surgeons introducing laparoscopy into their practice.

Reversed-Polarity Synthesis of Diaryl Ketones through Palladium-Catalyzed Direct Arylation of 2-Aryl-1,3-dithianes.

An umpolung approach to the synthesis of diaryl ketones has been developed based on in situ generation of acyl anion equivalents and their catalytic arylation. This method entails the base promoted palladium catalyzed direct C-H arylation of 2 The resulting 2,2-diaryl-1,3-dithianes with aryl bromides. Use of MN(SiMe3)2 (M=Li, Na) base results in reversible deprotonation of the weakly acidic dithiane. In the presence of a Pd(NiXantphos)-based catalyst and aryl bromide, cross-coupling of the metallated 2-aryl-1,3-dithiane takes place under mild conditions (2 h at rt) with yields as high as 96%. The resulting 2,2-diaryl-1,3-dithianes were converted into diaryl ketones by either molecular iodine, N-bromo succinimide (NBS) or Selectfluor in the presence of water. The dithiane arylation/hydrolysis can be performed in a one-pot procedure to yield a good to excellent yields. This method is suitable for rapid and large-scale synthesis of diaryl ketones. A one-pot preparation of anti-cholesterol drug fenofibrate (TriCor®) has been achieved on 10.0 mmol scale in 86% yield.

Base-Mediated Rearrangement of α-Dithioacetyl Propargylamines via Expansion of Dithioacetyl Ring: Synthesis of Medium-Sized S,S-Heterocycles.

Base-mediated rearrangement of 1,3-dithianyl-substituted propargylamines in DMF via expansion of the dithiane ring has been reported. The rearrangement provided 9-membered amino-functionalized sulfur-containing heterocycles (dithionine derivatives) in good yields under mild conditions. Propargylamines bearing 5-membered 1,3-dithiolane and 7-membered 1,3-dithiepane rings rearranged in a similar manner yielding 8- and 10-membered S,S-heterocycles, respectively.

Colour-responsive fluorescent oxy radical sensors.

A series of fluorene-fused benzoquinones (Q1-Q5) were prepared by thermolysis of 4-fluorenyl-4-hydroxycyclobutenones. Red fluorescence observed for Q2 is switched by reduction to blue fluorescence by formation of the hydroquinone. Reaction with hydrogen peroxide restores the original fluorescence colour. The potential use of compound Q2 as a reactive oxygen species detector is discussed.

History of suffocation, state-trait anxiety, and anxiety sensitivity in predicting 35% carbon dioxide-induced panic.

The aim of this study was to examine the effects of history of suffocation, state-trait anxiety, and anxiety sensitivity on response to a 35% carbon dioxide (CO2) challenge in panic disorder patients, their healthy first-degree relatives and healthy comparisons. Thirty-two patients with panic disorder, 32 first-degree relatives, and 34 healthy volunteers underwent the 35% CO2 challenge. We assessed baseline anxiety with the Anxiety Sensitivity Index (ASI) and State-Trait Anxiety Inventory (STAI1), and panic symptoms with the Panic Symptom List (PSL III-R). A history of suffocation was associated with greater risk of CO2 reactivity in the combined sample. Patients had more anxiety sensitivity and state and trait anxiety than relatives and healthy comparisons; the difference between relatives and healthy comparisons was not significant. In female patients, trait anxiety predicted CO2-induced panic. Having a CO2-sensitive panic disorder patient as a first-degree relative did not predict CO2-induced panic in a healthy relative. History of suffocation may be an important predictor of CO2-induced panic. Trait anxiety may have a gender-specific relation to CO2 reactivity.

A Novel Ferrocenyl Naphthoquinone Fused Crown Ether as a Multisensor for Water Determination in Acetonitrile and Selective Cation Binding.

A multisensor which is based on a novel multifunctional triad molecule, ferrocenyl naphthoquinone fused crown ether (Fc-cnq) bearing ferrocene, quinone, and crown ether functional groups together, was synthesized and characterized in this study. Sensing performance of a trace amount of water and the selective cation binding capabilities of this multisensor were carried out by the electrochemical, spectroelectrochemical, and spectrophotometric titration techniques in acetonitrile (CH3CN). It was shown that the potential separation (E((Fc))1/2 - E((2))1/2) between the second reduction of naphthoquinone and the oxidation processes of ferrocene in the triad molecule Fc-cnq was proportional to the amount of water due to the hydrogen-bonding interactions between water and the doubly reduced species (Fc-cnq(2-)). This property enabled Fc-cnq to detect the trace amount of water in CH3CN. The half-wave potential (E((Fc))1/2) of the ferrocene in Fc-cnq was used as an internal reference potential, and it defined the accuracy of the detection. In addition, by using the UV-vis spectrophotometric titration technique in CH3CN, it was also shown that the Fc-cnq multisensor could bind Ba(2+) and Ca(2+) cations selectively. We proposed that the intramolecular charge-transfer (CT) transition which occurred between the donor ferrocene and the acceptor naphthoquinone was the principle mechanism for the selective binding property of this multisensor. Quantum chemical calculations were also performed to investigate optical and electronic properties of the Fc-cnq molecule.

Warm Ischemia-Related Postoperative Renal Dysfunction in Elective Laparoscopic Partial Nephrectomy Recovers During Intermediate-Term Follow-Up.

PURPOSE: To analyze the impact of warm ischemia time (WIT) on early postoperative and ultimate renal function after elective laparoscopic partial nephrectomy (LPN). PATIENTS AND METHODS: One hundred and twenty-seven patients who underwent elective, ischemia-applied LPN were investigated in this study. The study patients were without stage 3 or greater chronic kidney disease (CKD) (estimated glomerular filtration rate [eGFR] <60 mL/min/1.73 m(2)) before LPN. Initially, the patients were grouped using the criteria of postoperative de novo stage 3 or greater CKD: Group A (n=104, eGFR ≥60 mL/min/1.73 m(2)) and group B (n=23, eGFR <60 mL/min/1.73 m(2)). The patients were also divided into two groups using 27.75 minute cutoff value obtained by receiver operating curve (ROC) analysis for WIT: Group 1 (n=69, WIT <27.75 min) and group 2 (n=58, WIT ≥27.75 min). The groups were compared with regard to demographic, perioperative, histopathologic, and renal functional outcomes. RESULTS: The decreased preoperative eGFR (P<0.001) and increased WIT (P=0.007), operative time (P=0.015), diabetes mellitus (DM) rate (P=0.019) and pathologic tumor size (P=0.031) were significantly different in group B. Multivariate analysis determined that independent predictors of de novo stage 3 or greater CKD in the early postoperative period were preoperative eGFR (P<0.001), WIT (P=0.014), and DM (P=0.030); meanwhile, preoperative eGFR (P=0.006) was the only independent predictor at last follow-up. Decreased median postoperative eGFR (P=0.018) and percent preserved postoperative eGFR (P=0.001) were significantly different in the increased WIT group, as well as elevated median postoperative eGFR loss (P=0.001). After similar follow-up (26 vs 23.5 months, P=0.913), the increased and limited WIT groups were not significantly different with regard to final eGFR (P=0.936), final eGFR loss (P=0.749) and percent preserved final eGFR (P=0.690). CONCLUSIONS: In elective LPN, increased WIT plays an important role in renal functional loss in the early postoperative period. This functional loss, however, recovered after an intermediate term follow-up period, similar to that of patients undergoing limited WIT.

Synthesis of diarylmethylamines via palladium-catalyzed regioselective arylation of 1,1,3-triaryl-2-azaallyl anions.

Diarylmethylamines are of great interest due to their prevalence in pharmaceutical chemistry. As a result, new methods for their synthesis are in demand. Herein, we report a versatile protocol for the synthesis of diarylmethylamine derivatives involving palladium-catalyzed arylation of in situ generated 2-azaallyl anion intermediates. The 2-azaallyl anions are generated by reversible deprotonation of readily available aldimine and ketimine precursors. Importantly, the arylated aldimine and ketimine products do not undergo isomerization under the reaction conditions. Scale-up of the arylation and hydrolysis of the resulting products to furnish diarylmethylamines were also successfully performed.

[A comparison between three irrigation methods in the debridement of contaminated bovine cancellous bone and the effect of duration of irrigation on the efficiency of debridement]. / Kirletilmis dana spongiöz kemiginin debridmaninda üç yikama yönteminin karsilastirilmasi ve yikama süresinin debridman üzerine etkisi.

OBJECTIVES: Irrigation and debridement constitute an important part of treatment of open fractures. We investigated the efficiency of different irrigation methods and durations in cleansing contaminated bovine femur cancellous bone samples and the extent of tissue damage associated with irrigation. METHODS: A total of 72 samples of 4x4x1 cm size were obtained from fresh frozen bovine distal femoral cancellous bone. The top surface of the samples were sawed to a 2-mm depth to create four squares equal in size. All the samples were contaminated with construction sand using the same method and were then randomized to three irrigation groups (bulb syringe irrigation, high-pressure pulsatile lavage, and low-pressure pulsatile lavage), each consisting of 24 samples. The duration of irrigation was set as 3, 6, or 9 minutes for every eight samples of each group. After the irrigation procedure, the images were transferred to a computer screen with a video-microscope camera and the number of sand particles on the samples were counted and irrigation-related macroscopic bone damage was assessed. RESULTS: The lowest number of sand particles was found on the samples irrigated by high-pressure pulsatile lavage (p<0.001). The duration of irrigation did not affect the efficiency of cleansing in all the groups (p>0.05). The least irrigation-related bone damage was observed in samples irrigated by low-pressure pulsatile lavage for 3 minutes (p<0.01). The amount of bone damage was similar in all groups after irrigations beyond 3 minutes (p>0.05). CONCLUSION: Our findings showed that the most efficient method of cleansing contaminated bone samples was high-pressure pulsatile lavage and that prolonged irrigations did not enhance the efficiency of the irrigation method; however, high-pressure irrigation of 3 minute duration resulted in the greatest bone damage.

Diels-Alder reactions of novel (1'-arylallylidene)cyclopropanes with heterodienophiles.

Palladium-catalyzed cross-coupling of various aryl iodides with bicyclopropylidene provided isolable (1'-arylallylidene)cyclopropanes, which reacted with a number of carbonyl compounds in the presence of Eu(fod)3 under high pressure to furnish oxaspiro[2.5]octene derivatives in moderate to good yields (22-69%). The reactions of the allylidenecyclopropanes with two azo compounds as dienophiles afforded diazaspiro[2.5]octenes in high yields (82 and 99%) even at ambient pressure. When treated with nitrosobenzene, two of the allylidenecyclopropanes gave the Diels-Alder adducts in up to 83 and 40% yield. 2,5-Diiodo-p-xylene coupled twice with bicyclopropylidene, and the product underwent a twofold Diels-Alder reaction with nitrosobenzene to produce the bis(spirocyclopropaneoxazine) derivative in 88% yield. This overall transformation can be brought about in a one-pot, two-step operation by addition of the nitrosoarene to the reaction mixture immediately after formation of the allylidenecyclopropanes to furnish various 5-oxa-4-azaspiro[2.5]oct-7-ene derivatives in 22-77% yield. The coupling of methyl bicyclopropylidenecarboxylate with 2,6-dimethylphenyl iodide produced a mixture of very stable regioisomeric allylidenecyclopropane derivatives in 90% yield. The reaction of this mixture with N-phenyltriazolinedione gave a corresponding mixture of the spirocyclopropanated heterobicycles in 61% yield.